DE2244908A1 - PERMSELECTIVE POLYMERIC MEMBRANES - Google Patents

Description

Permselective polymeric membranes

The invention relates to permselective polymeric membranes for selective separation of fluid mixtures and a process for their preparation. The invention particularly relates to permselective membranes containing a linear polymer which Contains N-ary! Substituted benzimidazole units, and a process for the production of such permselective membranes.

It has long been known that specific constituents are separated, purified or concentrated in a fluid mixture can by reverse osmosis using a membrane or boundary layer with permselectivity.

Lately reverse osmosis or reverse osmosis methods have been used Osmosis process in the production of pure water from sea water or from salty water or other impure water or by treating waste water and drainage more prominently, as there is an increasing need for safety of water supplies or resources and there is pollution should be avoided and as little energy as possible should be used.

309813/1062 The separation processes, in which the perine selectivity of such

Membranes used has dor in the fields of dialysis electrolytic dialysis and ultrafiltration brought about great developments with oils. Research work was carried out with the Aim taken to find suitable substrates for such membranes to create and to provide methods for the production of such membranes.

The quality of such permselective membranes is the most important factor in the separation process, in which a reverse osmotic Membrane is used, and in order to achieve effective separation with membranes of this type it is imperative that the membrane has a characteristic permselectivity.

The membrane should have such a characteristic property, that it enables a specific liquid medium to flow through it in a fluid mixture, but that the other components cannot penetrate. If a separation is carried out using such a membrane, this must have a high mechanical strength that is sufficient withstand the high operating pressure, and it must also have a sufficiently practical penetration speed own. The membrane must still have the ability to maintain these desired properties for an extended period of time. The membrane is required to be chemically and physically stable for a long time under the operating conditions is.

With the increasing importance of the reverse or.mose separation method, many attempts have been made to develop substrates suitable for such membranes having the desired properties, and various membrane substrates have been proposed. However, these conventional membranes do not show any; high permeability or high desulination activity, even when they are used for the linU-mxiioralisicruss or Entr.n1 / .unR of fioov / ar.ütrt odor unh'.hal 1U ¹ ^ m Warsscr, and their stability; IIJT not ro high DAFL they used in industriollem scale during längeror tent ^first

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SAD ORIGINAL

v / can ground. It has been assumed that of the known membranes an asymmetric cellulose acetate membrane made by Loeb and Sourirajan (see US Pat. No. 3,133,152) was that is the best. However, a cellulose acetate membrane of this kind easily hydrolyzed under acidic or alkaline conditions or by microorganisms similar to eggs, resulting in a Brings deterioration in properties. It therefore only has a limited useful life. In addition to this disadvantage is that their use is limited. Cellulose acetate membranes of this type are therefore not satisfactory.

Recently, permselective membranes have been made that use a nitrogen-containing polymer as a substrate, such as a fully aromatic one , Polyamide or polyhydrazide have been proposed (see, for example, US Pat. No. 3,567,632).

Typical examples of polymers containing nitrogen described in this U.S. patent include, for example Polymetaphenylene-isophthalamide-terephthalamide copolymers and polyisophthaloyl hydrazide. Although in this literary fool it is described that the benzimidazole ring can be contained in a chain of aromatic polyamides is not taught that nitrogen-containing linear polymers, the N-aryl substituted Benzimidazole units contained in the main chain, air, substrate polymers suitable for pcrmselective polymeric membranes are.

The invention relates to permselective polymeric membranes which have excellent permselectivity and which the Permeability of water in an aqueous solution with high aoGchwindickoit large, which, however, do not let dissolved substances through. The invention also provides a method for Manufacture of such permsolective membranes.

The invention relates to pcrmsclektivo polymeric membranes, which have excellent permselectivity and the ebunfn] Jr. nu.igezeichnoi.c physical and chemical

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- It _

Properties such as strength, Young's modulus, chemical stability and the like.

The invention relates to a method for producing such permselective polymeric membranes as well as a permselective polymeric membrane, which the excellent permselectivity during a long time under the operating conditions and which can be easily manufactured from a substrate «and a Process for the production of such permselective polymeric membranes.

The permselective polymer membrane according to the invention contains im essentially a linear polymer that acts as the main structural units Contains N-aryl-substituted benzimidazole units. (1) The linear polymer consists essentially of repeating Units represented by the following general formula I:

wherein A is a divalent atomic moiety of the following general Formula II

Ar-.

means, in which m and η represent O or 1, the two stick /

carbon atoms on two adjacent nucleus carbon atoms of the group]

Ar ^ are bonded and Ar ^ is a monovalent aromatic group /

with up to 15 carbon atoms and in which (i), if η /

O means, Ar ^ a trivalent atomic group with up to 15 Koh- j

lens toff at omen, Y the group -COIiU-, -COlIHNHCO-, NHCONH- and (.

-NHCNHNHC- mean, and if Y means -COlJH- or -NHCNHIlHC-, "

ti Il MM ₁

0 0 0 0 \

j, Ar ^ can be bonded both to the nitrogen and to the carbon atoms of Ys (ii) if η - 1 is at the bottom, —ι —r— is a single bond, Ai'j is a monovalent aromatic group with ';

309813/1082;

up to 15 carbon atoms and Y is an atom group which is represented by the following formula III.

H ^/ III

V.

mean, where the two nitrogen atoms are attached to adjacent core carbon atoms of the aromatic group Ar-. are bound and Ar-, a monovalent aromatic group of up to 15 carbon atoms means; and (iii) the divalent atomic group represented by the above formula II in the polymer both can be bound in the left as well as in the right directions.

(b) B represents a single bond or a divalent organic bond Group in which the average atomic number with exception of hydrogen atoms is not greater than 80 and carbon atoms are present in both terminal ends, and when B is a single bond, contains the repeating unit A is the atomic grouping represented by Formula II above.

(2) The parameter (Hp) of the hydrophilic property expressed by the following formula of the linear polymer is at least 0.4 '

N "ι- 10N ₁ .

Total number of atoms excluding ^{J of} the hydrogen atoms in the polymer

where I-L, the number of hydrogen bonding units (hydrogenbonding units) by polar groups in the entire molecule provided v / ground, means, and by the product of the number (Na) of hydrogen linking groups in the total Polymer and its hydrogen bond strength (G ,,) expressed becomes and M, the number of ionisohon groups In dom total Polymers mean with the Proviso that the number of ionic Groups not 1 per "fj () O dor» Uoli.'kulat'ReuIchts dos polymeric over-

( 3 0 ¹ J 8 1 1/1 0 6 2

strides;

* ■ ■ ■ ■

(3) the solubility at 25 ° C of the linear polymer in a solvent such as Ν, Ν-DImethylacetamid, N-Methy! Pyrrolidon, Dimethyl sulfoxide or hexamethylphonophoramide, at least 7 wt. is (with the solvent up to 5% by weight of lithium chloride may contain) and

(4) the linear polymer has a molecular weight that is sufficient is to form a movie.

In summary, it can be said that the permselective according to the invention polymeric membrane contains a linear polymer, the main structural units of which are N-aryl-substituted benzimidazole units contains, the linear polymer meeting the following requirements:

(1) The linear polymer contains, as main structural units, N-aryl-substituted benzimidazole units, which are represented by the Formula II above are shown, namely the following formula Ha

^N c-

XIa

wherein m is 0 or 1, or the following formula IEb

Ar ₁ C-

1K ¹ MI 'lib

I I Ar. Ar ^

(2) The above-defined parameter (Hp) dti · hydrophlic Um Klgschaft der, linear polymers is at least O, ^f l, preferential,. «·. · Weis» at least 0.5 ·

a «j /

(3) The linear polymer has a certain degree of solubility (at least 7% by weight) in a solvent which mainly contains dimethylacetamide, N-methylpyrrolidone, DimethyIsulfoxyd and Hexamethylphosphoramid (and where the Solvent lithium chloride as a dissolving aid in an amount not exceeding 5% by weight), and

the linear polymer has a molecular weight sufficient to form a film.

The above requirements (1) to (4) to be met by the permselective polymeric membrane of the present invention are given below described in more detail.

(1) Structure of substrate polymer

As described above, the substrate polymer contains the permselective repeating units of the polymer membrane

following formula

It is not necessary that A and B be different, however

at

B can be bound to a large number of groups A, for example from a few groups A to many groups to A (from several to scores of A's). It is also possible that the number of Groups B is 0 and that the polymer only contains A units contains. In short, A may be an atomic group having the N-aryl-substituted structure represented by the above formula II is shown, namely the above formula ITa or Hb, and B is a bonding moiety that connects the atomic groups of A to each other connects.

As explained above, the above formula II can be written as follows will:

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-2-

t ■

Ar ^Ar 2

Ar ₁ "V

When m in the above formula Ha is 1, the formula Ha can be expressed as follows:

-Y-Ar / ^N c- Ha-I

^ls N ^y
ι
Ar ₂

and when m is O, the formula Ha is expressed as follows :

" ^Ar 1, _N , ^C ; IIa-2

The divalent atomic group A of formula ii can be represented by any the above formula Ha-I, IIa-2 and lib.

In these formulas Ha and Hb or Ha-I, IIa-2 and Hb, Ar «means a trivalent or tetravalent aromatic group and Ar ₂ and Ar- mean a monovalent aromatic group. Each of these aromatic groups Ar ^, Ar «and Ar ^ contain up to 15 carbon atoms. Furthermore, these groups can be substituted by such substituents as lower alkyl groups, lower alkoxy groups, halogen atoms, nitro groups, sulfonic acid groups, carboxylic acid groups, lower alkoxycarbonyl groups or salts of these acid groups.

Y in the above formula Ha or Ha-I denotes a group of following formulas

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-COIiH- (or -NHOC-), -CONHNHOC-,

-NHCONH- and

-NHCNHNHC- (or -CMNHCHiI-)

Il Il - II 11

0 0 OO

and the number of the group Y ₃ contained in the unit A is not particularly critical. One Y or two or more Y groups can be present in unit A.

Atomic groups A expressed by the above formulas Ila and Hb are, do not have to be the same, and two or more various residues A can be present in the polymer chain. The units of A can be Ha or Hb in the above formula in reverse as shown in Formula Ila or Hb is to be included. ·

As mentioned above, B can be either a single bond or a chain bond of the structural units A. The unit B can be any divalent organic group if only the average number of atoms except hydrogen atoms is not greater than 80 in the entire polymer chain.

It is preferred that the substrate polymer as unit A at least Contains one of the groups represented by the following formulas: ■

A./V

Ar,

-Ar »

^Xv N '

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or

-NHOC-Ar "

wherein Ar ¹ ^ and Ar " _{2 are} a group of the following formula:

V-a

Vb or

(R ₁ U

where R * is a hydrogen or a halogen atom or a lower alkyl group or lower alkoxy group with 1 to 3 carbon atoms, £ 1 or 2 and Z is a single bond or an alkylene group with up to 4 carbon atoms, -0-, -S-, - SOg- or -CO- and, when Z represents a single bond, the formula Vc represents a trivalent or tetravalent diphenyl group and ^M ... "in the aromatic group represents a single bond in the case of Ar ¹ ^ and a hydrogen atom or a substituent R ^ in the case of Ar "^.

For the units B it is preferred that the substrate polymer contains as units B:

(1) at least one kind of divalent organic groups,

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such as (i) aromatic hydrocarbon radicals containing a benzene or Contain naphthalene nucleus, (ii) aliphatic hydrocarbon radicals, which contain a cyclohexane, cydopentane or cyelobutane ring, (iii) straight-chain or branched, saturated ones or unsaturated hydrocarbon radicals with 1 to 6 carbon atoms and (iv) 5- or 6-membered heterocyclic radicals, which contain oxygen, nitrogen or sulfur and which can be condensed onto a benzene ring, with the terminal Ends of the divalent organic groups are present, or

(2) (a) at least one type of bivalent, trivalent or tetravalent organic groups, the carbon atoms being present in the two terminal ends and originating from the radicals mentioned in (i) to (iv), and _t

(b) the organic groups with at least one type of binding

divided, such as -0-, -S-, -SO ₂ -, - CO-, -N- (where R is a hydrogen atom or an alkyl group with 1 to 3 carbon atoms or a phenyl group), -COHN- ', -CONHNHOC-,

-C

-NHCHN-, -CONHNHCOHN- and> N are bound and where the

Atomic groupings (1) and (2) through a lower alkyl group with 1 to 4 carbon atoms, a lower alkoxy group with 1 to 4 carbon atoms, a halogen atom, a nitro group, an acid or carboxyl group, a salt of an acid residue, a lower alkoxycarbonyl group, a primary, secondary or tertiary amino group, an ammonium salt thereof or a quaternary ammonium base can be substituted, and wherein in the Units B present throughout the polymer, the average number of atoms excluding the hydrogen Atoms is not larger than 80, preferably not larger than 50.

The following are particularly preferred as substrate polymers:

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(i) Polymers in which the units A have at least one type of di valent groups expressed by the following formula:

are wherein Ar'o and Ar ¹ ,, which may be the same or different, are a monovalent aromatic group having up to 15 carbon atoms », expressed by the formula

VI-I

VI-2

mean, in which R "and R", which can be the same or different, a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a halogen atom, a nitro group, a sulfonic acid or carboxylic acid group or a salt thereof, ρ is 1 or 2 and Z has the definitions given above for formula V-c and wherein the units B have at least one kind of divalent organic group expressed by the following formula,

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- + W -

22A4908

VII

(Sp) p

where q ^ is an average content of the units

contained in the polymer,

and has a value of 0.2 to J> moles per mole of the repeating units A, R ₂ and ρ have the definitions given above for formula VI-I and W -COM- (which can also be in the opposite direction), -0-; -SO-,

-CO

"S.

N- (in this case the Ur or ß-ring is trivalent),

-CO

-CONHNHOC-, an alkylene group with 1 to 4 carbon atoms or

-N-

ji N

! I Ι -C C- V.

means?

wherein X is -0-, -S-, -NH-, or

(R ₂ ) P

(II) Polymers in which the units A have at least one type of divalent Atomic groupings represented by the following formula,

-COHIi

C-

VIII-I

Ar '.

or

-NHOC-,

A,

C-

VIII-2

0 9 8 13 710 6 2

contain, wherein Ar ¹ ,, has the definitions given in the above formula VI, and the units B have at least one kind of atomic groupings which are represented by the following formula,

IX

(RJp

where q ~ is the average content of the units (R ₂ ) P

TS tf ~ means and a value from to 5 moles per mole of the repeating units A and Rp, ρ and W have the definitions given in formulas VI and VII: and

(III) Polymers in which the units A have at least one type of Mean atomic groupings expressed by the following formula X. will

wherein Ar ' _{2 has} the definition given above for formula VI and the units B mean at least one type of atomic groupings which are represented by the following formula Xl

XI

are expressed in which q ₂ , R ₂ * P and W have the definitions given above for formula IX.

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(2) hydrophilic property

The substrate polymer used in the present invention, which has the above-mentioned structure, should be a hydrophilic one Parameter (Hp) of at least 0.4, preferably of at least 0.5 *. Polymers that have a hydrophilic parameter (Hp) of at least 0.55 are particularly preferred in the present invention. '

As mentioned above, the parameter (Hp) can be of the hydrophilic property from the following formula

N ₁₁ + 10N _T

Total number of atoms, excluding

the hydrogen atoms in the polymer be calculated.

It is known that a polymer to be used as a substrate for permselective material must be hydrophilic to some extent. The parameters NU and N _T , which are used to calculate the para-

± 1 X

meters (Hp) of the hydrophilic property according to formula IV is used are, for example, in the following Mtneraturstellen

A) Gordy, Stanford, "Journal of Chemical Physics", Vol. 9> Pages 204-214 (March 1941) and

B) U.S. Patent 3,567,6 ^ 2 described.

As can be seen from the above formula IV, the hydrophilic parameter (H) of the polymer is given by the ratio of the sum of (i) the hydrogen bond strength, based on different polar Groups contained in the substrate polymer and (ii) the number of ionic groups contained in the substrate polymer are expressed in terms of the number of the number of atoms excluding hydrogen atoms in the substrate polymer.

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In formula IV it is defined that N _{H interprets} the number of bonded hydrogen units, which are supplied by polar groups in the total molecule, expressed as the product of the number ('hydrogen bonding groups (N _ft ) in the total' polymer and their hydrogen bond strength or Hydrogen bonding strength (Gy) and N- mean the number of ionic groups in the entire polymer, with the proviso that "the number of ionic groups does not exceed 1 per 500 molecular weight of the polymer.

Methods for calculating the N », Gy and Njj values are in the above cited references A and B described in detail. In Table I are values of N », Gy and Nj, of typical polar ones Groups specified.

Tabel 1 Polar groups

Ny V N 1 2 2 1 4th 4th 1 6th 6th 1.5 2 3 1.5 4th 6th 1.5 6th 9 2 4th 8th

Ketone «more aliphatic-aromatic
Kther and d! Aromatic kther

dieliphatic ether

Amino, substituted amino and
Hydroxyl

Beter, SuIfon and SuIfoxyd

Imidazole

Oxadiazole

The number of ionic groups in the overall polymer, i.e. the Ν * value, can easily be calculated from monomeric compounds, used to make the substrate polymer. Typical cases of ionic groups present in the substrate polymer of the permselective membrane according to the invention include -SO- * H, -SO, Me (where Me is an alkali metal or an alkaline earth metal means), -COOH, -COOMe (where Me means the above Definition), an ammonium salt and a quaternary ammonium salt. It is preferred that the number of ionic groups

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1 or less than 1 per 500 of the molecular weight of the substrate polymer amounts to.

(5) solubility

It is essential that the substrate polymer of the permselective polymer according to the invention meets the requirement that the solubility at 25 ° C in a solvent which contains at least one of the following compounds: Ν, Ν-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and hexamethylphosphoramide (where the lithium chloride solvent may contain in an amount equal to 5%) does not exceed at least 7 wt -. is -%. It is preferred that the substrate polymer has a solubility value of at least 10 · wt -.% Has.

The substrate polymer is not required to have solubility s value of at least 7 wt .- ^, based on all four solvents; it is sufficient that the polymer has a solubility value of at least 7 wt .- ^, based on one of the four aforementioned solvents. A sol- ' Ches solvent can also contain lithium chloride as a dissolving aid in an amount which does not exceed 5 wt .- ^.

(4) Average molecular weight

The substrate polymer of the permselective membrane of the present invention should have an average molecular weight (an average degree of polymerization) sufficient to form a film. To meet this requirement, it is preferred that the substrate _{polymer have an inherent viscosity (^ J n} J ₁ * determined at JO ⁰ C) in a solution of the polymer in N-methylpyrrolidone at a concentration of 0.5 g / 100 ml of at least 0.4, especially at least 0.6.

Process for making substrate polymers comprising the above Meet requirements (1) to (4) will now be explained in more detail.

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22AA908

(5) Preparation of substrate polymers

Substrate polymers used in the present invention and the N-aryl substituted benzimidazole units can be produced, for example, by a process that has been described by the same applicant, for example, according to a method described in US Pat. No. 3,518 23 ^ (corresponding to British Pat. No. 1,236,211) has been described.

This process for producing the substrate polymers will now be explained in more detail below.

An aromatic triamine or tetramine that is represented by the following formula

^ NH H _? N-Ar ₃

NH 1

HN NH ₂

HN ^ "NH XII-2

I 1

Ar * Ay *

is represented in which Ar «, Ar ₂ and Ar-, the definitions given above in the above formula II have, is reacted with (a-1) an aliphatic, allyclic, aromatic or heterocyclic dicarboxylic acid or a reactive derivative thereof, wherein a polyamidimine is formed, for example, repeating units expressed by the following formula

HN-Ar ₁

XIII-I

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■ - 19 -

- NHC-B «-C

KH S

XIII-2

contains, wherein B * means a hydrocarbon radical which derived from the dicarboxylic acid or its reactive derivative, and this polyamide-imine is then subjected to cyelodehydration thrown, for example, by the polyamide-imine tnüfc an acid treated or heated and with an N-ary! substituted polybenzimidazole that contains repeating units represented by the following formula

-HN-Ar ₁ CB · -C

' yr NN

"" HC ^ ^kT \ ^ C-B'-f XIY-2

V. N ^ - N '

A Tr · A v »

Ar ₅ Ar ₂

are expressed in which Ar-, Ar ₂ , Ar, and B ^{1 have} the definitions given above.

Preferred examples of N-ary! Substituted aromatic triamine or tetramine of the above formula XII-I or XII-2, which for Production of the structural units A of the substrate polymer according to the invention are used, are described in more detail below.

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* (1) N-aryl-substituted "aromatic triamines of the above formula

2,4-diaminodiphenylamine 2,4-diaminophenylnaphthylamine 4- {2,4-diaminoanilino) «- benzophenone 4- (2 _# 4-DImaihoaniiino) -diphenylether · 4- (2,4-diaminoanilino) -bipheny1, l-anilino- S ^ -dlaminonaphthalene 2 ~ anilino-1,5-diaminonaphthalene 4-anilino-3 _# 4 ^t -diaminodiphenyl -3 # 5-dianiinodipheny 1

δ-diaminodiphenyl ether 4-anilino-3,3'-diaminodiphenyl sulfone 4-anilino-3 # 3'-diaminobenzophenone 3-anilino-4,6-diaminodiphenylmethane

(2) M-aryl substituted aromatic tetramines of the above formula XII-2:

1,3-DianIlino-4,6-diaminobenzene i 3 * -Di-p-toluidino-4,6-diaminobenzene i »3-BIs- (p-chloroanilino) -4,6-diaminobenzene 4 * 4'-DianilIno- 3 * 3 ^l -dianilinodiphenyl 2,6-DianilIno-1,5-diamino-naphthalene 2,2'-bis- (4-anilino-3-aminophenyl) -propane 4,4 * -dianilino-3,3'-diaminodiphenylether 4, 4'-Dianilino-3 # 3'-diaminodipheny1-sulfone 4,4'-Dlanilino-313 ¹ -diaminobenzophenone.

Preferred examples of the dicarboxylic acid or its reactive derivative formed with an N-aryl-substituted aromatic triamine or tetramine, as listed above as examples, can be implemented are given below:

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(i-a) Aromatic dicarboxylic acids:

Terephthalic acid

Isophthalic acid

2,6- or 1,5-naphthalene-dicarboxylic acid 3 * 3'- or 4,4'-diphenyldicarboxylic acid 3, ^ '- "or 4,4'-diphenylmethane-dicarboxylic acid 3,3'- or 4.4 ^l * Diphenyl ether dicarboxylic acid 3,3'- or 4,4'-DiphenyIsulfon-dicarboxylic acid

3,3'- or 4,4! · -Dipheny 1- (2,2-propane) -diearboxylic acid

3,3'- or 4,4'-benzophenone dicarboxylic acid

(i-b) Alicyclic dicarboxylic acids

1,3-cyclohexanedicarboric acid 1,4-cyclohexane dicarboxylic acid

l * 3-cyclopentane dicarboxylic acid.

i, 3-cyclobutane dicarboxylic acid

(i-c) Aliphatic dicarboxylic acids:

Oxalic acid
Succinic acid
Adipic acid
Fumaric acid

(i-d) oxygen-, nitrogen- or sulfur-containing 5- or 6-membered heterocyclic dicarboxylic acids:

2,4- or 2,5-pyridine-dicarboxylic acid 2,4- or 2,5-purane-dicarboxylic acid 2,4- or 2,5-thiophene dicarboxylic acid

(i-e) Reactive derivatives of dicarboxylic acids (i-a) to (i-d): halides, especially chlorides, lower alkyl esters and phenyl esters of the above-described dicarboxylic acids of (i-a) to (i-d), such as the reactive derivatives thereof used. Acid chlorides are generally preferred as reactive derivatives, and the use of aromatic di-, carboxylic acid chloride is particularly preferred.

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- ²² - 22U908

Is used in the production of the above polyamide imines, including an aromatic one N-aryl-substituted triamine or tetraamine, as indicated above, with a dicarboxylic acid or a reactive derivative of which, as indicated above, is implemented, a polyfunctional part Compound as explained below in the reaction system present, a substrate polymer is obtained which copolymerized with such polyfunctional compounds. Such a polyfunctional compound can be given as examples name: (a) aminocarboxylic acids, tricarboxylic acid monoanhydrides, Tetracarboxylic acid dianhydrides and their reactive derivatives, (b) diamines, hydrazines, aminohydrazides and aminodihydrazides, (o) Dihydroxy! compounds and Aminohydroxy! compounds and (d) diisocyanates and masked diisocyanates. When copolymerized Polyamidimines by reaction between aromatic N-ary! Substituted trlamines or tetraamines with the dicarboxylic acids or their reactive derivatives in the presence of a polyfunctional one Compound, as mentioned above, the cyclodehydration are subjected, a substrate polymer is obtained of the type of copolymer containing structural units A and B.

The armonic triamine or tetramine, which by the above Formula XII-I or XII-2 is represented, forms the main part the structural unit A of the substrate polymer used in this invention and the dicarboxylic acid component of (i-a) bis (i-e) and the polyfunctional compound component of (a) to (d) form the main part of the structural units B of the substrate polymer. In this case, the amine component, the dicarboxylic acid component and the polyfunctional compound component not limited to one kind, but two or more kinds of each component can be used.

For example, an amino group, such as an aminocarboxylic acid, react a diamine or an amihohydrazine with a carboxylic acid chloride or a similar compound, with a 0

Amide bond (-CNH-) is formed. You can use cyclic anhydride groups, such as tricarboxylic anhydride or tetracarboxylic acid di-

309813/1062

react anhydrides with an amino or isocyanate group, with

1!

an imide bond ("^^ N-) is formed. A hydrazine,

Il

a dihydrazide or similar compounds with a carboxylic acid chloride convert, whereby diaeylhydrazide bonds 0 O

11 Il

(-CNHNHC-) are formed. The hydroxyl group of a dihydroxy1 compound is reacted with a carboxylic acid chloride, wherein

Il

an ester bond of (-CO-) is formed. Will be an isocyanate reacted with a carboxylic acid, forming an amide bond, and an isocyanate group is converted to an amino group

sets, forming a urea bond (-NHCNH-). These bonds are introduced into the substrate polymer as structural units B. The diacylhydrazide bond that is in the unit B may be included in a 1,3,4-oxadiazole bond

(-C C-) can be converted by cyclodehydration.

If Il

N N

It is also possible to create an o-hydroxyamide linkage by reaction between an amino hydroxyl compound such as 2,4-diaminophenol, and an acid chloride to produce and this bond

to be converted into a benzoxazole bond (- \ \\ CJ by cyclodehydration.

The nature and amount of the components which make up the major part of Unit B of the substrate polymer should be selected so that the average number of atoms excluding hydrogen chloride atoms present in a unit B in the entire substrate polymer are included, not greater than 80, preferably not greater than 50, and that the value of the above-mentioned parameter Hp of the hydrophilic property is at least 0.4. It is also necessary that these components are selected so that

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• - 2 * -

that the above-mentioned requirement of solubility of the emerging Substrate polymer is met.

Preferred examples of polyfunctional compounds (a) to (d) will now be explained.

(A) aminocarboxylic acids, tricarboxylic acids, tetracarboxylic acids and their reactive derivatives: "

(a-1) aminocarboxylic acids and their reactive derivatives, such as m- and p-aminobenzoic acids, 6-amiho-2-naphthoic acid, 4-AmInO-diphenylmethane-dicarboxylic acid, 3-aminobenzophenone-carboxylic acid, fc-aminocarboxylic acid and its amino acid chlorides, hydrochlorides.

(a-2) Tricarboxylic acid anhydrides and their reactive derivatives, such as tri-mellitic acid monoanhydride, naphtha] in-2,3,6-trioboic acid monoanhydride, 2 # 4,4'-diphenylmethane tricarboxylic acid monoanhydride, l * 2,5-Cyclohexan-tricarboxylic acid monoanhydride and monochloride monoanhydrides of these acids.

■ *

(a-?) Tetracarboxylic acid dianhydrides and their reactive derivatives, such as pyromellitic acid dianhydride, 2,3,6,7-naphthalene-tetracarboxylic acid-dlanhydride, 3,3 *, ^, ^ '- Diphenylmethane-tetracarboxylic acid-dlanhydride, Cyclobutane-tetracarboxylic acid anhydride, 1,4,5,8-naphthalene-tetracarboxylic acid anhydride and their reactive derivatives.

(b) diamines, hydrazines, aminohydrazides and dihydrazides, such as aliphatic ^ diamines, e.g. B. Ethylenediamine, Tetramethylendlamln, Hexamethylene diamine and octamethylene diamine; alicyclic diamines, for example 1, J-DIaminomethylcyclohexane, 1,4-diamino methylcyclo hexane and ^, ^ '- diaminodicyclohexylmethane; aromatic diamines, for example m-phenylenediamine, p-phenylenediamine, 1,5-naphthalene diamine, 2,6-naphthalenediamine and diamines of the formula

(where X is a single bond, a

Alkylene group having 1 to 4 carbon atoms, -O- or -SOp-); Piperazine, 2,4-diamino pyridine and 2,5-diamino pyridine; m-aminobenzoic acid hydrazide and p-aminobenzoic acid hydrazide;

2,5-diaminofuran, 2,5-diaminothiophene

309813/1062

and isophthalic acid dihydrazide and terephthalic acid dihydrazide.

(c) Dihydroxy compounds such as ethylene glycol, tetramethylene glycol, Hexamethylene glycol, cyclobutanols 1,4-cyclohexane-dimethanol and p-xylylene glycol; and aminodihydroxy compounds, such as Ethanolamine, p-hydroxymethylaniline, 3,3'-dihydroxyberizidine, 2,4-diaminophenol and 1,4-diamino-2,6-dihydroxybenzene.

(d) Diisocyanates, such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate and 2,6-naphthalene diisocyanate, and masked products of these diisocyanates.

N-aryl-substituted polyamide benzimidazoles, expressed by the Formula XIV-I above, N-aryl-substituted polybenzimidazoles, expressed by the above formula XIV-2, and copolymers that containing mainly these polymers can be prepared according to the method of the aforementioned US Pat. No. 3,518,234 (corresponding to British Patent 1,236,211) or a modified one Process thereof can be produced. In the present invention, substrate polymers prepared according to other methods than those produced above can be used if they satisfy the above-mentioned requirements (1) to (4). The method of U.S. Patent 3,518,234 is thereby characterized in that the desired polymer consists of a polyamine-1min is obtained. In other words, the process for making the N-aryl substituted benzimidazole linkages is severed performed by the Polymer Manufacturing Implementation. at Other methods of forming the suicide polymers can be used in the present invention. For example, you can Polymers represented by Formula XIV-2 and XIV-I above can be prepared by adding a tetramine or triamine, such as represented by the above formula XII-2 or XII-I, with a dicarb.onic acid diaryl ester polycondensed with heating according to the method described in "Journal of Polymers Science", Al, I53I (1963). According to the procedure outlined in "Makromolekulare Chemie", 77, 41 (1964)

309813/1062

Polymers represented by the above formula XII-2 can be made by making a diaraine that has an N-ary! substituted Contains benzimidazole group represented by the following formula,

Ar, Ar ₅
HJI-Ar. -C Ar, C-Ar. -HH- XII-3

where Ar ^ and Ar _{2 have} the definitions given above for formula II and Ar * represents a radical which is derived from an aminocarboxylic acid as listed in (a-1) above, reacts with a dicarboxylic acid or a similar compound .

Substrate polymers other than those defined by the above formulas XIV-I and XIV-2 can be shown, for example, according to the following procedures.

For example, N-aryl-substituted polybenzimidazoles, containing the following repeating units

XIV-3

wherein Ar * and Ar _{2 have} the definitions given in Formula II, prepared by the process described in "Journal of Polymer Science", 0, 511 (1961) with an N-aryl-substituted aromatic diaminomonocarboxylic acid, which by the following formula is shown

NH-

Ar-

309813/1062

ORIGINAL INSPECTBD

22AA9Ü8

wherein Ar 1 and Ar _{2 have} the definitions given above for formula II and Q is -OH, -OR (where R is a lower alkyl group, a phenyl group or another hydrocarbon radical) or -NH ₂ , or on a reactive derivative thereof causing self-condensation with heating. »

In some cases, polybenzimidazoles containing repeating units of the formula XIV-Ji alone do not meet the solubility requirement (3) In such a case, the solubility and the hydrophilic property can be achieved by using such triamines or tetramines represented by the formula XII-I or XII-2, and / or polyfunctional compounds as mentioned in (a) to (d) above, copolymerized to give substrate polymers which can be used in the present invention.

When a diamine and a dicarboxylic acid or an aminocarboxylic acid or a reactive derivative thereof may be used as comonomers to obtain a polymer, wherein a part of the repeating units of this polymer by the following formula

~ j- IiHC-Ar '

are represented, wherein Ar ^ and Ar _{2 have} the definition given above and .Bj. means a group derived from the polyfunctional compound added as a comonomer component.

Becomes a compound of the above formula XII-4 with a dicarboxylic acid -dichloride reacted in a molar ratio of 2: 1, an amidimine-dicarboxylic acid is obtained which is represented by the following formula

309813/1062

O O

Il Il

NHC-Bp-CHH

Q-OC-Ar ₁ ^ * ^N Ar ₁ -CO-Q

^X NH HN '

»I

wherein Ar 1, Ar ₂ and Q have the definitions given above and B _{2 represents} a dicarboxylic acid residue or a derivative thereof, and when this amidimine dicarboxylic acid or the derivative thereof is subjected to cyclodehydration, an N-aryl-substituted one is obtained Benzimidazole dicarboxylic acid represented by the following formula

Q.OC-Ar, CB - C ^N Ar, CO.R XH-6 Ar_ Ar ₂

wherein Ar-, Ar ₂ , B ₂ and Q have the definitions given above, or a derivative thereof. When such a compound represented by the formula XII-5 or XII-6, or a reactive derivative thereof, is reacted with a diamine as indicated in (b) above, ß in the case of the compound of the formula XII-5 the cyclodehydration is then carried out and a polybenzimidazole is obtained which has repeating units, each containing two repeating units of the above formula XIV-4 which alternate with one another in an inverse manner, namely repeating units represented by the following formula

{WHOC-Ar, ^ * CB ₃ -C * ^N Ar ₁ -CONH-B ₁ . 4-

I «" XIV-5

Ar

in which Ar ₁ , Ar ₂ , B _{2 have} the definitions given above and B 1 denotes a diamine radical.

309813/1062

In this method, preferred examples of the Q group are aryl-r oxy and -NHg groups. If Q means -OH, so is it possible to convert this into the corresponding dicarboxylic acid chloride and then to react this with a diamine »If Q means -OH, it is possible to produce a polyamide-benzimidazole, which has repeating units of the formula XIV-5 by a diisocyanate as exemplified in (d) above was used in place of the diamine.

An amine hydrazide represented by the following formula

H ₀ NHNC-Ar, A

^NH YTT 7

I ΛΙΙ-7

wherein Ar 1 and Ar _{2 have} the definitions given above, can be obtained by reacting a compound of the above formula XII-4 with hydrazine according to known methods. Similarly, a benzimidazole hydrazide represented by the following formula can be used

HNHNC-Ar / '^ CB -C * ^ Ar ₁ -CNHNH ₀

^{2 1} ^ N- " ² ^ N ' ^{λ 2} XII-8 ι. I ■
Ar ₂ Ar ₂

wherein Arj, Ar ₂ and B _{2 have} the definitions given above, are prepared by reacting a compound of the above formula XII-6 with hydrazine.

A compound of the above formula XII-7 can be converted into a polyamideimine hydrazide the following formula

ί ° ° NHP-R T_

I ti ti j, NHC-B ₂ 4-.
—Τ CHNHNC-Ar ₁ *

^{k N} NH ^J

309813/1062

224490 *

Are converted in which Ar 1, Ar 1 and B _{2 have} the definitions given above when it is reacted with a dicarboxylic acid chloride at low temperatures according to the method of US Pat. No. 3,389,122. If the polyamideimine hydrazide thus formed is subjected to cyclodehydration, a polybenzimidazole-oxadiazole can be obtained which has repeating units of the following formula

C C-Ar / ^ CB-4- v _{Q /} Ix _n / 2J

XIV-6

Ar ₂

contains, wherein Ar ^, Ar ₂ and B _{2 have} the definitions given above.

Some of the polymers, which are mainly repeating units, which are represented by the above formula XIV-6, meet the above solubility requirement (3) not. In such a case, polybenzimidazoles are formed, which are mainly repeating units that are formed by the can be expressed using the following formula

1 ° ° π 11

- + ■ CNHNHC-Ar

XIV-7

contain, wherein Ar ", Ar ₂ and B _{2 have} the definitions given above, according to a phenomenon which occurs when the cyclization of an amidimine bond to a benzimidazole ring and the cyclization of a diacylhydrazide bond to a '1,3 ^ -oxadiazole bond are simultaneously in the presence carries out an acid catalyst, the former cyclization generally proceeding preferentially.

309813/1062

A polybenzimidazole semi-arbazide containing repeating units, which are represented by the following formula

H-NHCONHNHCO-Ar _n CB _D -C Ar _n CONIINHCONH-

! 1

Ar ₂ Ar ₂

■ 4

contains, in which Ar ^, Ar ₂ and B _{2 have} the definitions given above and B ^ denotes a diisocyanate group, can be prepared by reacting a compound of the above formula ΧΪΪ-8 with a diisocyanate.

You can also make a polybenzimidazole urea, which has repeating units of the following formula

KHA /

r ν ν ° Ί

4 HNCKHAr / ^ C-Bg-cf jAr ^ NHCNH-B -L
I ¹ ^ B ' ² / H; ". ■> XIV-9

Ar ₂ Ar ₂

where Ar 1, Ar ₂ ", B ₂ and B are the definitions given above
if you have a bezimidazole diamine, for example
following formula

N-Ar /
² lK ^{2 X} N ^ ^{λ 2}

V XII-9

HN-Ar / ^ CB ₅ -C ^v Ar, .- NH ^{2 lx 2 λ}

wherein Ar ^., Ar ₂ and Bp have the definitions given above, is reacted with a diisocyanate.

Preferred compounds that are used to form an N-aryl substituted aromatic monocarboxylic acid monoamine group, the
is expressed by Ar ^, in compounds given by the

309813/1062

the above formulas XII-4 to XII-8 are to be introduced, are compounds represented by the following formulas

⁵⁰⁰ CX

NH

and

NH ₂

wherein Q is as defined above and X is -0-, -CH ₂ -, '-SO ₂ -, -S- and -CO-.

In the cyclodehydration of polymers which have N-aryl-substituted aromatic triamine or tetramine structural units of the preceding formulas XIII-I, XIII-2 or XIII-J, not all of the atnidimine parts have to be converted into N-aryl-substituted benzimidazole units. It is sufficient that at least about 50 $, preferably at least about 70 $, of the amidimine moieties are cyclodehydrated to N-aryl substituted benzimidazole units.

Preferred process conditions for the Preparation of sub-polymers according to the invention, in which N-aryl-substituted triamines or tetramines, by the above Formulas XII-I or XII-2 are used , as described previously in US Pat. No. 3,518,254 or British Patent 1,2J6,211.

309813/1062

Are aromatic triamines and / or tetramines, as mentioned above, with dicarboxylic acid halides in a solvent system containing an inert organic solvent such as methyl ethyl ketone, cyclohexanone, tetrahydrofuran or tetramethylene sulfon and an aqueous alkali solution, or in a solution polymerization system that has a low temperature , such as a weakly basic solvent such as N-methylpyrrolidone, hexamethylphosphoramide or Ν, Ν-dimethylacetamide, reacted, the corresponding polyamide imines are formed. If these Polyamidimine heated for several hours in a solid state at a temperature exceeding 200 ⁰ G, preferably 250 to 300 ⁰ C, or they are in solution at 60 to 20O ⁰ C in the presence of an acidic compound such as cresol, acetic acid, formic acid, Phosphoric acid, sulfonic acid, sulfuric acid, boric acid and hydrochloric acid, heated, cyclodehydration occurs and the N-aryl-substituted benzimidazole polymers are obtained. A preferred method for carrying out the above reactions is a method in which a polyamideimine is formed in a weakly basic aprotic polar solvent as mentioned above and the polyamideimine thus obtained is heated in solution and cyclized by using the as a catalyst Used hydrogen halide, which is obtained as a by-product in the reaction in which the polyamideimine was formed, and the polyamideimine is converted into the desired N-aryl-substituted benzimidazole polymer. In this preferred method, the hydrogen halide remaining in the system can be converted into a lithium halide or a potassium halide by adding an oxide or hydroxide of lithium or calcium, and such a metal halide can be used as a swelling agent in the preparation of the membrane from the N- ary! substituted benzimidazole polymer can be used. This embodiment is described in more detail below. In the cyclization step, in order to control the catalytic activity of the hydrogen halide, a lower alkylene oxide can be added in order to convert part of the hydrogen halide into a halohydrin. .

Are polyfunctional comonomers in the above implementation

309813/1082

Ingredients as mentioned above are used to obtain substrate polymers of the copolymer type, the N-aryl-substituted Contain benzimldazole units. The comonomer components are appropriately selected depending on the particular uses of the resulting permselective membrane.

In addition to these copolymers, mixtures of polymers, containing various ingredients as mentioned above can also be used in the present invention.

Any N-aryl substituted benzimidazole homopolymers and copolymers, which satisfies the above requirements (1) to (4) can be used regardless of the manufacturing method for forming the permselective membrane according to the invention can be used.

According to the invention, according to the aforementioned various Process N-aryl-substituted benzimidazole polymers are produced which meet the following four requirements:

(1) They contain N-aryl-substituted benzimidazole units, those represented by the formula II, namely the formula Ha or Hb will.

(2) The above-defined parameter (Hp) of the hydrophilic property these polymers is at least 0.4, preferably at least 0.5-

O) Their solubility at 25 ⁰ C in one of the following solvents Ν, Ν-dimethylacetamide, N-methylpyrrolidone, dimethyl sulphoxide and hexamethylphosphoramide or mixtures thereof (with the solvent lithium chloride may contain in an amount 5 wt -. $> Does not exceed ) 7 wt .- # and

(4) They have a molecular weight sufficient to form a film.

The above substrate polymers of the present invention have the N-aryl-substituted benzimidazole units represented by the above Formula Ha or Hb are represented, and as these units

309813/1062

Containing polar groups, as shown in Table I, such as imidazole, AnId and substituted amino groups, these substrate polymers are essentially hydrophilic. This hydrophilic property can be adjusted in a suitable manner by selecting suitable groups for Ar ^, Ar ₂ and / or Ar * in the formulas Ha or Hb, the types or proportions of the comonomers which are used to form the units B of the substrate polymers used, selected accordingly or regulated in a suitable manner the degree of cyclodehydration of the polyamideimines obtained as an intermediate or their copolymers. An appropriate number of polar groups as indicated in Table I, such as hydroxyl, amino, sulfone and oxadiazole groups, can thus be introduced into the substrate polymer.

If the amounts and types of Ar ^, Ar ₂ and Ar ^ groups and / or the comonomer components are appropriately regulated and selected, the amounts and types of other terminal groups contained in the substrate polymer, such as -SO -jH, -SO-zMe, -COOH, -COOMe, ammonium salt and / or quaternary ammonium salt (where Me means an alkali metal or an alkaline earth metal) can also be easily adjusted and controlled.

According to the invention it is possible to use substrate polymers with suitable to produce hydrophilic properties, namely a substrate polymer which has a parameter (Hp) of the hydrophilic property of at least 0.4, preferably of at least 0.5.

Since the substrate polymer of the present invention has N-substituted aryl groups contains, the molecular weight range is wide within a suitable range, and therefore the present invention possesses Substrate polymer increased solubility and a suitable permselectivity. The solubility of the substrate polymer in a solvent, as mentioned above in connection with requirement (j5) can be adjusted or regulated by measuring the degree of cyclodehydration of the intermediate product Pqlyomidamins or its copolymer regulated, or by the types and amounts of the comonomoron constituents to appropriate Manner and selects, according to the invention, a substrate

3Ο9Β13 / 1ΟΠ2

polymer which in a solvent, as mentioned above, has a solubility of at least 7% by weight , preferably of at least 1% by weight. The fact that the substrate polymer of the present invention has such a solubility indicates not only that its processability in making the membranes is good, but also that if the substrate polymer has an appropriate solubility (affinity) in such polar solvents as Ν, Ν-Dimethylacetamide, N-Methy! Pyrrolidon, Dimethylsulfoxyd and Hexamethylphosphoramid, it has, if it has been processed into a membrane, a suitable permselectivity.

Process for making membranes from the aforementioned Substrate polymers will now be described in detail.

(6) Manufacture of membranes *

The permselective membranes according to the invention can be produced by forming a film from a solution which is mainly

mainly N-aryl-substituted benzimidazole homopolymers or copolymers, as previously described in an organic polar solvent.

Preferred solvents used to form the membranes are aprotic polar solvents, in particular so-called amide-like solvents, such as N-methy! pyrrolidone, N-methylcaprolactam, N, N-dimethy1formamide, Ν, Ν-dimethylacetamide, Hexamethylphosphoramide and tetramethylurea, and sulfonic and sulfoxide-like solvents such as dimethyl sulfoxide and tetramethylene sulf on. It is particularly preferred that such an aprotic polar solvent have a dielectric constant (£) of at least 15.

When preparing a polymer solution using a such, as mentioned above solvents, the solubility, the drying properties, the solidifying properties and other properties can be adjusted by adding a suitable diluent. As such, diluents are used

309813/1062

preferably used for example: water, methanol, ethanol, Chloroethanol, ethylene glycol, chloropropanol, ethyl acetate and Chloroform, It is preferred that such a diluent be used in such an amount that the substrate polymer, the is dissolved in the aprotic polar solvent does not precipitate and that the film does not lose its transparency during the membrane forming step.

According to the invention, a method is preferably used in the formation of the permselective membranes, which consists in using a solution which (a) a linear substrate polymer containing the above-mentioned N-aryl-substituted benzimidazole structural units, and (b) an aprotic organic solvent as indicated above which has the ability to dissolve the substrate polymer, or a mixture of the solvents with a diluent as indicated above (such solvents and mixtures thereof are hereinafter referred to as "aprotic organic solvents"), and if desired together With (c) a low molecular weight compound which is soluble in both the organic solvent (b) and a non-solvent (d) mentioned below and which has a molecular weight not exceeding 500, partially solidified to such an extent that the resulting partially solidified product "self-sustains" zend is "to a non-solvent for the linear substrate polymers dipping the partially solidified product in (d) that is compatible with the polar organic solvent and reacting at least 75 wt. ->% of the polar organic solvent (b) is extracted or of the polar organic solvent (b) and the low molecular weight compound (c) remaining in the partially solidified product. According to the invention, permselective membranes are obtained which have excellent permselective properties.

The preferred method according to the invention for producing the permselective membranes will now be explained in more detail below ".

3098 13/1062

According to the invention, the substrate polymer (a) containing the above-mentioned repeating N-aryl-substituted Behzimidazole units is dissolved in the aprotic organic solvent (b) in such an amount that the polymer concentration is about 7 to about 50 wt .-; U, preferably about IO to ungefährl 35 percent -. $> is. So can a suitable amount of diluent, as mentioned above, before or after
added to the dissolution of the substrate polymer. The dissolution of the substrate polymer in the polar organic solvent occurs at a suitable temperature within a
Range from room temperature to 10O ⁰ C.

It is preferred to use inorganic salts such as lithium chloride, lithium bromide, lithium nitrate, Calcium chloride, calcium bromide, calcium nitrate and magnetic

■ ι ■ ■

sium perchlorate, and organic compounds such as urea,
Ethylene glycol, glycerin and formamide are added as low molecular weight compounds (c) which are soluble in both the aprotic polar solvent (b) and the nonsolvent (d) for the substrate polymer (a) and which have a molecular weight that does not exceed 500. Inorganic salts as mentioned above are particularly preferred as the low molecular weight compounds (c).
The low molecular weight compounds (c) can be dissolved in the aprotic polar solvent (b) at any time. One can have such a connection with low
Molecular weight (c) in the organic solvent (b),
dissolve during or after the dissolution of the substrate polymer (a) in the solvent (b).

The solution thus formed, which the substrate polymer (a) and the
aprotic polar solvents · (b) contains, optionally together with a compound (c) of low molecular weight, is partially solidified by separating a part of the solvent therefrom and removed to such an extent that the substrate polymer in the solution acquires the self-supporting property and wherein a partially solidified membrane of the
Substrate polymer (a) is obtained.

309813/1062

It is preferred that such a partially solidified membrane contain 200 to 25% by weight, especially 150 to 50% by weight, of the aprotic polar solvent (b) or the solvent (b) and the low molecular weight compound (c) , based on the substrate polymer (a), in the partially solidified membrane. It is also preferred that the amount of the low molecular weight compound present in the starting solution is less than 50 wt%, particularly 5 to 30 wt% , based on the substrate polymer.

The preferred temperatures for partially drying to obtain a partially solidified membrane vary depending on the type of solvent, casting thickness, drying time, the rate at which air is introduced for drying, and other factors. But if the solidification is carried out according to the drying method, preferred temperatures in the range of 30 to 200 ° C, in particular from 80 to 150 ⁰ C.

In making the above-mentioned partially solidified membranes, it is possible to deform them into a suitable shape. For example, not only can the substrate polymer be formed into a film, but a thin coating can also be formed on a porous plate or on a substrate material or on hollow fibers, and so on. When the permselective membrane is to be formed as a film, the above-mentioned solution is poured onto a tape or plate. If a porous ¹ substrate material is used, the substrate material is with

..the solution for example with coating rollers, by spraying, with Uber.zugs-,

/ devices or coated by immersion. If a membrane is to be formed on the hollow fiber, the solution is extruded from spinnerets for hollow fibers. You can do the above Solution to partially solidified films or membranes according to dry or wet methods, or a combination process by dry and wet processes.

According to the present invention, the partially solidified product thus formed becomes of the substrate polymer, which is self-supporting, into a non-

309813/1062

Solvent <d) dipped, the organic with the aprotlschen polar solvent (b) is compatible, but which the substrate polymer (a) it does not dissolve, and in this case be at least 75 wt -.% Of the residual solvent (b) or at least 75 wt. -% of each of the solvent (b) and the low molecular weight compound (c), when contained in the solvent (a), extracted and separated from the partially solidified membrane. It is preferable that this extraction takes place to such an extent that 80 to wt -.% Of the residual solvent or 8o to 100 wt .- ^ of each of the remaining solvent and the compound can be separated with low molecular weight. A permselective membrane according to the invention is thus obtained.

Preferred examples of non-solvents (d) used for immersing the partially solidified film or membrane include, for example, water, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol and glycerin, and aqueous solutions of such alcohols. The use of water, methanol, ethanol or an aqueous solution of methanol or ethanol is particularly advantageous. In general, the extraction is preferably carried out at a temperature in the range of -20 to +50 ⁰ C. If the immersion extraction is carried out at too high a temperature, although the extraction rate can be accelerated, care must be taken because the properties of the membrane may be deteriorated by loss of transparency and binding of heterogeneous parts in the membrane. Generally, the immersion extraction is carried out for a time sufficient to remove at least 75% by weight of each of the remaining solvent and the low molecular weight compound from the partially solidified film or membrane. It is preferred that after the extraction step the membrane formed is stored in water and that this state is maintained in the membrane. In general, the water content of the membrane is about 25 to about 75% by weight ,

309813/1062

The water content of the membrane is determined according to the following equation calculated:

Weight of the water in the "

. Water content (*) = _χ

Weight of the wet membrane

In some cases, when the membrane is treated with hot water of 70 to 95 ° C after the immersion extraction step, you can the properties such as desalination ability can be further improved.

In the present invention, when the low molecular weight compound (c) is in the solution of the substrate polymer (a) is present in the aprotic polar organic solvent when the partially solidified membrane is immersed in the non-solvent (d) not only the organic solvent (b) but also the low molecular weight compound (c) extracted and partially solidified from the Separated membrane. The result is permselective membranes with a very fine porous structure, which increases the permselectivity the membrane is further improved.

As in the case of cellulose acetate membranes reported by Loeb et al (see US Pat. No. j5 153 1 ^ 2) the substrate polymer according to the invention can be shaped into a permselective membrane with an asymmetrical structure, namely a double layer structure that includes a dense top layer and a thin, relatively porous layer. For example one can use the method in which the moist film is formed, first of all, bring only one film surface into contact with the non-solvent (d), and in doing so becomes on on this side the degree of solidification accelerates. In the case of the dry process, the solvent is preferably from evaporates from a membrane surface, and while some of the solvent still remains in the membrane, the membrane becomes immersed in the non-solvent (d) to remove the residual © solvent and the like. In case where it is necessary 1st to add a low molecular weight compound (c), 309813/1062

i.e. an inorganic salt or an organic salt or an organic compound that differs from the organic solvent, based on the average size and the evaporation rate, differs, the permselectivity of the resulting membrane can be greatly improved by removing such a low molecular weight compound (c) in the extraction step.

The permselective membrane according to the invention generally has a thickness of 2 to 400 μ. In the event that the membrane has a PiIm shape, the thickness of the membrane is 10 to 400 μm, preferably 40 to 200 μm. The hollow fiber has μ generally an outer diameter of 20 to I50, a thickness of 5 μ to 40 and a void ratio (void ratio) of 0.1 to 0.6.

The permselective membrane of the present invention can be easily manufactured and it shows good water permeability and desalination properties when used for desalination or demineralization of sea water and salty water according to reverse osmosis -Process is used .. The membrane from the substrate polymer is chemically very stable and has excellent properties mechanical properties. It can be used for a very long time, and even under high pressure it shows good dimensional stability, and the water permeability is only slightly decreased. The permselective membrane of the present invention therefore has a very high great practical value.

When the permselective membrane of the present invention is used for desalination or demineralization of sea water or saline water according to the reverse osmosis method, it exhibits such excellent permselective properties that the water permeability Wp 5 to IjX) is O (? / M / hr. Χ atmosphere , and the salt retention is 40 to 99 * 8 %. The water permeability and the salt retention are determined according to the following formulas:

30981 3/1062

Water permeability _ Amount of permeated water (Lit ^ r) ₁ bility VJp Membrane area ( _m ^) χ time (hours) χ pressure ~

(Atmosphere)

q-, '-Ir- salt concentration in solid

halteyermögen = (1- ^x ^ 'material was used

In determining the water permeability "Wp" according to the above

Formula means the pressure (atm) the actual reverse osmosis pressure, ie (^ p - ATC) y whereAp is the difference in hydraulic pressures across the membrane and ΔTC is the difference in osmotic pressures across the membrane.

The permselective membrane according to the invention clearly differs from the membrane of the aforementioned U.S. patent 3,567,632. The substrate polymer of the permselective Membrane contains N-aryl-substituted groups in the main chain and by the presence of the N-aryl substituted groups the permselective membranes according to the invention have a high permselectivity which is better than that of the permselective membranes Membranes according to U.S. Patent 3,567,632. From the following Examples can be seen that a comparison of poly (metaphenylene-isophthalamide / terephthalamide) copolymers a typical example of a substrate polymer according to the US patent with the polyamide-benzimidazole according to the invention shows that the Polymers according to the invention can be processed more easily into a membrane. The permeability properties, in particular the permselective permeability of a membrane formed from the polymers according to the invention is significantly better than that of a membrane made from the polymers of US Pat was produced.

The permselective membrane of the present invention is effective not only for desalination or demineralization of sea water or salty water, but also for the treatment of toxic waste water from paper mills or pulp mills, Plating works and similar plants

309813/1062

to separate radioactive waste water that comes from Atomic piles or similar, and for the separation or concentration of different components in the pharmaceutical, biochemical and food industries. The permselective membrane according to the invention can also be used in dialysis and electrolytic dialysis, and is widely used in other fields.

The following examples illustrate the invention, but without it to restrict.

example 1

According to the method as described in US Pat. No. 3,518,234, a polyamide with an inherent viscosity of 0.85 (determined at JO ⁰ as a solution of 0.5 g of polymer in 100 ml of N-methylpyrrolidone® is as follows the values of the inherent viscosity, unless otherwise stated, determined in this way) from terephthaloyl chloride and 2,4-diaminodiphenylamine by polycondensation using a methyl ketone water system. The Polyamidimin was treated ⁰ C for 3 hours in a nitrogen atmosphere at 280 to JOO, to give a Polyamldbenzlmidazol inherehten with a viscosity of 1.93. It was found by IR adsorption spectrum analysis that the conversion to the polyamide-benzimidazole was more than 95 % , and this polymer had repeating units represented by the following formula

OCIIN

It was found by calculation that the hydrophilic parameter (Hp) of the polymer was 0.65. When the Nr / s "value of this polymer according to the method described in US Pat. No. 3,567,632

309813/1082

driving was calculated, the above value was found to be 12 ',

and thus the polymer obtained in this way no longer fell into place of the US patent.

This polyamide-benzimidazole was dissolved in N-methylpyrrolidone so that the polymer concentration was 15% by weight, and then lithium chloride was dissolved therein in an amount of 20% by weight based on the weight of the polymer. The resulting solution was filtered with a microfilter and poured to a thickness of 60 μ on a smooth glass plate at room temperature using a doctor blade. The infused material was dried for 15 minutes at 130 ⁰ C and then immersed in methanol at J50 ° C for about 30 minutes together with the glass plate. The film . was peeled off the glass plate and immersed in a large amount of water at room temperature for one night.

The membrane produced in this way was transparent and looked dark brown. The thickness of the membrane was 33-36 p and the water content was 56 %! A part of the resulting membrane was cut, dried and subjected to atomic absorption analysis. The amount of residual lithium chloride was found to be less than 0.003 % . ■,

The wet membrane was used in a reverse osmosis device, which in particular was built so that it had a pressure up

ρ ρ

endured up to 150 kg / cm. The area of the membrane was 11.3 cm. A carrier with a pore size of 5 p- containing a sintered stainless steel disk and filter paper was used. The membrane was attached in such a way that the surface exposed to the. first stage of the membrane-producing upon drying in contact with air, was the solution side was adjacent to a high pressure "A salt solution having a concentration of 0.105% (atm with an osmotic pressure of 0.75 as measured at 25 ⁰ C) was added at the Permeability test used, the at 25 ⁰ C and a pressure of

10 kg / cm ^{2 was} carried out.

309813/1062

" ⁴⁶ ~ 22U908

The amount of water which permeated through the membrane was determined periodically, and the salt concentration of the permeated water was determined conductometrically to determine the salt retention capacity. As a result, it was found that the water passage was 5.4 t / m / hr. and that the salt retention was 95 % and the water permeability Wp was 1,050.

The above experiment was repeated in the same way except that the surface which had been in contact with the air was arranged so as to delimit the side with the high pressure solution. The amount of water that penetrated was found to be 6.0 t / m / h. The salt retention was 93.5 % and the water permeability Wp was 1140. It can be easily seen that the membrane prepared in this example shows good water permeability and high desalination activity even at a pressure as low as 6.0 kg / cm.

A membrane, which was prepared in the same manner as described above, was exposed to hot water at 80 ° C during Treated for 5 minutes and then examined in the same way as described above. Was the front (the surface, those during membrane production when the solvent evaporates was in contact with air (the back side means the surface opposite to the front side) attached so that it has the

If the solution was limited by high pressure, the amount of water penetrating was 3.0 l / m / hour, ie the retention capacity was 98 % and the water permeability was 570. If the reverse side of the solution side was exposed to high pressure, the amount of water penetrating was 3.2 t / m / h, the salt retention capacity was 94 % and the water permeability was 610.

A copolyamide with an inherent viscosity was used for comparison of 1.6o from 100 mol- # m-phenylenediamine, 150 mol- # terephthaloyl chloride and 70 mole # isophthaloyl chloride prepared by solution polycondensation at low temperature, wherein one an N-methylpyrrolidone system according to that in the US patent

309813/1062

3,567,632 used. . Then, a 15 weight percent solution of the copolymer in N-methylpyrrolidone, which was 20 wt -% lithium chloride, based on the weight of the polymer ₃ contained prepared. A colorless, semi-transparent membrane with a thickness of 40 to 44 μ was formed from this solution, using the drying and immersion conditions described above.

The resulting membrane was subjected to the same permeability test at a pressure of 6.0 kg / cm using a 0.105 saline solution. When the front side confined the high pressure solution side, the water flow rate was 2.2 C / m ² / hr, the salt rejection was 28 %, and the water permeability was 420. When the back side of the membrane was exposed to the solution side with high pressure, so the water inflow was 2.5 l / m / h and the salt retention capacity was. 9.4 % and the water permeability was 477.

This membrane was also treated with hot water at 80 ° C. for 5 minutes and examined in the same way as above. When the front of the solution side was exposed to high pressure, the water flow rate was 1.0 & / m / h, the salt retention evermögen was 50 %, and the water permeability Wp was 190. When the back was arranged to delimit the solution side with high pressure, the water flow rate was 1.65 ^r -i / m ² / hr, the salt retention was 41 % and the water permeability V / p was 314.

Example '2

Following the same procedure as described in Example 1, a copolyamide-benzimidazole with a hydrophilic parameter Hp of 0.61 and an inherent viscosity of 1.45 was prepared from 100 mol- -3 terephthaloyl chloride, 80 mol- $ 2.4 -Diaminodiphenylamine and 20 mol $ 4,4'-diaminodiphenyl ether prepared, and this copolymer was then dissolved in N-methylpyrrolidone so / that. the copolymer was I5 wt. ~%.

^v - 309813/1062 -.

Calcium chloride was then added and dissolved homogeneously in the solution in an amount of 20% by weight , based on the weight of the polymer. A membrane was produced from this solution under the same conditions as described in Example 1.

The resulting membrane had a thickness of 23 µm and a water content of 65 * 5 %. As a result of atomic absorption analysis, it was found that the amount of calcium chloride remaining in the membrane was 0.019 % .

Using the same apparatus as in Example 1, the membrane was subjected to the permeability test at a pressure of 6.0 kg / cm using a 0.105 # saline solution. When the front surface of the solution side was subjected to high pressure, the water flow rate was 6.47 (/ m / hr, the water permeability Wp was 1230, and the salt retention was 93 % The amount of water was 6.37 l / m / hour, the water permeability was 1210 and the salt retention capacity was 92 %.

Example 3

A 3 * 5 # saline solution (with an osmotic pressure of 24.5 atm, determined at 25 ° C.) was placed in the same reverse osmosis device that was described in Example 1. A membrane prepared in the same manner as described in Example 2 was attached thereto, and then the permeability test was carried out at a pressure of 100 kg / cm. When the face of the membrane was arranged to delimit the solution side with high pressure, water flowed in an amount of 27 * 3 l / m / hr. through, the water permeability was 362 and the salt retention was 97 fo. When the back of the membrane was attached so as to delimit the solution side with high pressure, the water inflow was 33 * 5 l / m ² / h, the water permeability was 445, and the salt retention was 89 %.

309813/1062

~ ⁴⁹ "22U908

Example 4

A 15% strength by weight solution of the copolyamide-benzimidazole from Example 2 in N-methylpyrrolidone was poured onto a glass plate and dried at 100 ° C. for 3 minutes. The Gießlihg was then eingi a 40 $ strength aqueous solution of calcium chloride at 100 ⁰ C for 10 minutes in '
transparent membrane received.

100 ° C immersed for 10 minutes, a yellow semi-

After immersion in a large amount of water for 3 days, the membrane was subjected to the reverse osmosis test at a pressure of 80 kg / cm at 25 ^° C. using a 3.5% saline solution. When the front side of the membrane was attached to delimit the solution side with high pressure, the water flow rate was 2.34 Ω / m / hr, the water permeability Wp was 42 and the salt retention capacity was $ 95. ^The membrane tested had a thickness of 10 ρ and a water content of 28 %.

Example 5

A solution containing 15 parts by weight of the copolyamide-benzimidazole from Example 2, 4.5 parts by weight of lithium chloride and 80.5 parts by weight of N-methylpyrrolidone was prepared and filtered with a microfilter, then the solution was poured onto a glass plate with a thickness of 350 μ poured. -Man dried while I5 minutes at 130 ⁰ C, and then the casting in water at room temperature during one day was immersed. The resulting membrane had a thickness of 75 / * and a water content of 67 #.

The membrane thus formed was used in the same reverse osmosis apparatus as in Example 1, and the Dürchlässigkeitsversuch was measured at 25 ⁰ C under 80 kg / cm carried out using an aqueous solution containing 1.0 wt -% of an inorganic. Salt as indicated in Table 2 below was used. The results are also given in Table 2.

309813/1062

22U908

Table 2

Kind of inorganic
Salt

LiCl
NaCl
CaCl,

LiNO,
NaNO,

Water inflow

1Ί.0

17.5 16.0 15.8

16.5

Water permeability (Pw)

195

222 220

185 230

Salt retention capacity

99.1 99.5 99.8 98.2

98.5 99.8

Example 6

A solution containing 6 g of the copolyamide-benzimidazole from Example 2 with an inherent viscosity of 1.45 and 1.8 g calcium chloride and 30 g N-methylpyrrolidone was poured onto a glass plate and heated for 15 minutes at 130 ° C in Air dried. The casting was immersed in a large amount of water at room temperature together with the glass plate to remove residual solvent such as calcium chloride therefrom. A membrane with a thickness of 28 μ was obtained in this way.

The membrane thus formed was in the same device as it is described in Example 1 is used, and the passage

Liquid test was carried out under a pressure of 80 kg / cm using a 1.05 # saline solution, the The temperature of the feed solution as indicated in Table 3 was varied. The results are also given in Table 3.

309813/1062

Table 3

Substrate polymer

Membrane thickness (ju) before application after application ■ application of the pressure pressure temperature of the feed solution
2 ££ öo

Water- salt water- '■ salt- water- c salt inflow back- inflow back- inflow' back - (^ / m / h hold- (i ^; / m ² / h hold- (£ / m ² / h hold-

fortune fortune fortune

benzimidazole

28

26th

96.6

₉ 2.0

45.5

CD CD OO

Examples 7-20

The permeability of a permselective membrane can also can be determined by direct osmosis against a solution with an osmotic pressure. To show this, the carried out the following experiments.

To a solution of N-methylpyrrolidone containing 15% by weight of the copolyamide-benzimidazole of Example 2, an inorganic salt or a low molecular weight compound as shown in Table 4 was added in the amounts shown in Table 4, and the resulting solution was cast according to the method described in Example 1 to form a membrane. The membrane thus formed was used as a diaphragm between salt water with a concentration of 4.0 parts by weight Jii (the osmotic pressure was 32.5 atm, measured at 25 ⁰ C), and uses pure water, and the water permeability rate and the salt permeability rate were at 25 ° C determined. The results are given in Table 4.

309813/1062

Additive Lot* * Tabel fr water 22Λ4908 0.005 Art 0 water
salary
the Thickness of the 0.010 at 1 membrane membrane
(b) SaIz- 0.013 game
No. LiCl 2 I8.fr 13th inflow inflow.
(jüg / oni / sek) (wr / cw ² / sek) 0.015 7th LiCl 5 21.8 5. 5.8 0.100 8th UCl 10 2fr .3 5 10.0 0.125 9 UCl 20th 50.6 17th 16.0 0.085 10 LiCl 1 5fr. 5 13th 57.0 0.053 11 CaCl ₂ 3 56.0 30th 150.0 0.09fr 12th CaCl ₂ 5 22.0 fr 295.0 0.23fr 15th CaCl ₂ 10 31.0 lfr 7.fr 0.263 lfr CaCl ₂ 20th 37.0 5 12.fr 0.003 15th CaCl ₂ 20th fr6.0. 18th frfr. 3 0.051 16 Mb (C10k) _ 15th 65.5 23 131.0 0.02fr 17th urea 20th 21.2 21 360.0 0.93 18th Glycerin 20th 2fr.3 18th 8.3 19th UCl 31.0 28 - 11.2 20th fr2 10.1 Ver _
same* 86

*: Aromatic polyamide prepared in Example 1 as a comparative polymer was used as the substrate polymer.

**: The amount of additive was based on percent by weight expressed in terms of the weight of the polymer.

309013/1082

Example 21

A solution of Ν, Ν-dimethylacetamide, which is a copolyamide-imine contained in a concentration of 15 wt .- ^, was 25 Terephthaloyl chloride, 75 mol- # isophthaloyl chloride, 80 mol- ^ 2,4-diaminodiphenylamine and 20 moles $ 4,4'-diaminodiphenyl ether produced, whereby a solution polymerization in the presence of Ν, Ν-dimethylacetamide at low temperature to the usual Way performed. Propylene oxide was then added to the solution in an amount equimolar to that of the hydrochloric acid, which was in the solution and heated the solution to 100 ° C. for 1 hour to convert the copolyamide-imine into the corresponding copolyamide-benzimidazole to convict. According to the IR analysis it was confirmed that cyclodehydration had occurred in the copolyamide-imine. The resulting copolyamide-benzimidazole had an inherent viscosity of 0.71 and a hydrophilic parameter of 0.61.

The resulting polymer solution was divided into two parts. Lithium chloride was used in part in an amount of 20 wt. based on the weight of the polymer. Then the two parts of the solution were poured separately onto glass plates, at 115 ° C for 15 minutes and dried in methanol at room temperature immersed together with the glass plate.

Using the membranes thus formed the permeability test at 25 ⁰ C and a pressure of 6.0 kg / cm was carried out wherein there was used a 0.105 JSS-salt solution. Each membrane was placed so that the face delimited the side of the high pressure solution.

The membrane made from the lithium chloride-free solution (containing small amounts of hydrochloric acid, propylene oxide and propylene chlorohydrin) had a thickness of 15 Ji and a water content of 25%. In the permeability test of the reader membrane, the water inflow was 0.50 l / m / h, the Wanser permeability Wp was 95 and the desalination ratio was 98.5 %.

309813/1062

The membrane which had been prepared from the solution containing 20% by weight of lithium chloride, based on the polymer, had a thickness of 18 μm and a water content of 5 %. m ² / hour, the water permeability Wp was 720 and the salt retention capacity was 97.6 ^.

Example 22 '■. ! :. ".

Following the polymerization procedure described in Example 1 became a polyamide-imine with the following structural units

OCHN-

made from 2,4-diaminodiphenylamine and isophthaloyl chloride.

Part of the polyamide-imine thus formed was subjected to cyclodehydration in the same manner as described in Example Ί , whereby a polyamide-benzimidazole having the following structural units

obtained, wherein more than 95 wt .- $ of the amidimine bonds in Amide-benzimidazole bonds were converted.,.

The NR / s ~ values of the polyamidimine: (1) Tv were made according to the procedure of the above-mentioned US Pat. No. 3,567,632, and it was found that this value was 6.5 ug and the polyamide-imine, thus fell under the scope of the US patent. The no / s "-

309813 / f§82 ^!

" ⁵⁶ " 22U908. '

The value of the polyamide-benzimidazole (2) was calculated and found that the value was 12 and that the polymer (2) was thus no longer covered by the aforesaid US patent. ■:

A solution containing 10 parts by weight of the polymer (1), 3 parts by weight Lithium chloride containing 87 parts by weight of N-methylpyrrolidone was prepared. Similarly, a solution that 10 parts by weight of polymer (2), 3 parts by weight of lithium chloride and 87 Parts by weight of N-methylpyrrolidone contained, prepared. Both Bö ^ üntgeh were poured on a glass plate, while at 130 ° C 15 minutes "dried and in water at room temperature during one day fenced in.

The membranes thus obtained derived from the polymers (1) and (2) were subjected to the permeability test at 25 ° C and subjected to a pressure of 80 kg / cm, which is the same Reverse osmosis device used as in Example 1 and a 1.0 # saline solution employed. The results are in table listed.

Table 5

Substrate polymer

Polymer with repeating polymer with repeating repeating Units (1) Units (2) (comparative sample)

Membrane thickness (μ) 48 52

Water content (#) 55 65

Wasserzuflußgßschwin- ji ■ * Ir ₇ ο

age (i / mVh.) * '?> ¹⁷ ' ^b

Water permeability Wp 60 248

Salt retention capacity _nrt «, _{AO r}

(£) 92.1 90.6

■ ■ i. ^£ 'j.

It can be seen from the test results in Table 5 that the N-aryl-substituted benzimidazole bond is the permselective one

309813 / i06i ^c '^

Properties greatly improved.

Example 23 '

According to the polymerization process described in Example 1, a copolyamide-benzimidazole was prepared from 80 mol- # 2,4-diaminodiphenylamine and 20 mol- # 3j3 ^! -Diaminodiphenylsulfon manufactured. This polymer had a hydrophilic parameter Hp of 0.61.

In the same manner as described in Example 1, a solution was obtained of the polymer in N-methylpyrrolidone with a polymeric concentration of 15 wt .- ^ and a membrane was made therefrom.

For comparison, a polyamide was prepared from 3i3 ^l * -diaminodiphenylsulfone ^v and terephthaloyl chloride according to the same process as described in Example 1. This sample was used as a comparative polymer. Using the polyamide thus formed, a membrane was prepared in the same manner as described above.

The two membranes produced in this way were subjected to the reverse osmosis test subjected at 25 ° C under a pressure of 80 kg / cm, using a $ 1.0 saline solution. The results are listed in table 6 *

Table 6

__ substrate polymer

Copolyamide-polyamide

benzimidazole (comparative sample)

Water content ($) 61 53,

Membrane thickness (ji) 53 50

Water inflow (^ / m ² / h) 32.8 17.6

Water permeability Wp 455 2 ¹ M

Salt Retention Capacity (#) 96.0 66.5

309813/1062

Example 24

According to the polymerization process and the heatingSrCyclodehydra-, The method of Example 1 was a copolyamide-benzimidaz oil with an inherent viscosity of 0.65 from 2.03 G (0.007 mol) !, S-Diamino - ^^ - dianilinobenzene, 0.324 g (0.003 mol) metaphenylenediamine and 2.03 g (0.01 mole) of isophthaloyle chloride. This polymer had a hydrophilic parameter Hp of 0.62.

Then 2.0 g of this polymer were homogeneously dissolved in a solution containing 20 g of N-methylpyrrolidone and 0.6o g of lithium chloride, and the resulting solution was poured onto a glass plate in a casting thickness of about 200 μ and placed in a dryer with a thermostat dried at 110 ° C until the amount of residual solvent was reduced to about 60 % . Then the casting was immersed in a large amount of ion-exchanged water for one day.

The resulting membrane had a thickness of 45 μ and a water content of 56 %.

Using the same reverse osmosis device as in Example 1, the reverse osmosis test of the membrane thus formed was carried out under the same conditions as described in Example 21. The water inflow was 20.8 l / m / h, the water permeability Wp was 29Ο and the salt retention capacity was 88 %.

Examples 25 to 35

Polymers containing the structural units indicated in Table 7 were made according to the polymerization procedures described below and membranes were prepared according to the conditions shown in Table 8. The results the permeability tests of these membranes are listed in Table 9.

309813/1062

Process for the preparation of the polymers

(I) 70 MoI-Ji 2,4-diaminodiphenylmethane and 30 Mpl-% m-aminobenzoic acid hydrazide were reacted with terephthaloyl chloride in N-methylpyrrolidone. The resulting polymer was precipitated in water and stored at 500 ° C. for 3 hours under reduced pressure to contain the desired polymer. The structure of the polymer was determined by infrared absorption analysis. Observing the characteristic absorption 'lines of the oxadiazole ring at 1080 cm. and the characteristic absorption lines of the N-substituted imidazole ring were observed at 1320 cm and "1380 cm.

(II) A polymer was prepared by adding 70 mol- ^ 2,4-diaminodiphenylamine and 30 mole isophthaloyl dihydrazide with terephthaloyl chloride "implemented in the same manner as described in (I) above.

(III) A copolyamido-imine was prepared from 75 mol- $ terephthaloyl chloride, 25 mol- $ fumaric chloride and 2,4-diaminodiphenylamine 'according to the interfacial polymerization method using a methyl ethyl ketone-water system, and then the resulting polyamidoamine was converted into N- Methylpyrroiidon, which contained a small amount of hydrochloric acid, dissolved, and then the solution was ^{stirred at 120 °} C. for 2 hours; the desired polymer was obtained. The structure of the polymer was determined by IR analysis.

(IV) 80 mol Si 2,4-diaminodiphenylamine and 20 mol Ji 2,4-dimino-4'-carboxydiphenylamine hydrochloride were polymerized with terephthaloyl chloride in N-methylpyrrolidone. Calcium hydroxide was added to the resulting polymer solution in an amount sufficient to neutralize 95 percent of the hydrochloric acid present in the solution. The solution was then stirred for 2 Stunäen 12'0 at ⁰ C to give the desired polymer containing .:

(V) 20 MoI-Si 4-chloroformyl-N- (3-chloroformyl) phthalimide of the following formula

309813/1062

^Cloc coca

8O MoI-St * terephthaloyichloride and 100 MoI-J (J 2, "4-Diaminodiphenylamln were polymerized and cyclodehydratislert in the same way - as described in Example 1, and a polymer received.

(VI) A polymer was made from 4- (2,4-diaminoanilino) diphenyl ether and terephthaloyl chloride prepared according to the procedure described in Example 1.

(VII) A polymer was prepared by adding 70 l, 3-diamino-2,4-dianilinobenzene and 30 mol-ji 3,3'-Dlamlnodiphenylsulfon with terephthaloyl chloride according to the procedure described in Example 1 reacted.

(VIII) The polymerization and cyclodehydrate solution were carried out in the same way as described above under (IV), where one 75 mol-ji l ^ -diamino ^ i ^ -dianilinobenzene, 25 mol-j6 used m-aminobenzoic acid hydrazide and terephthaloyl chloride. It was confirmed by IR analysis that among those used Cyclodehydration conditions mainly the N-phenylbenzimidazole ring was formed and conversion of the hydrazide to the oxadlazole ring hardly occurred.

(IX) According to the in "Journal of Polymer Science", *> 0.511 (I96I) The process described, the melt condensation was carried out, with 70 mol-jU of 3-amino-4- (N-phenyl) -aminobenzoic acid phenyl ester and 30 moles of m-aminobenzoic acid pheny reads he used.

(X) As in the examples of U.S. Patent 3,389,122 described method, polyamldimine hydrazide was produced,

309813/1082

by 3-amino-4- (N-4-biphenyl) aminobenzoylhydrazide with Terephthaloyl chloride converted into N-methyl! Pyrrolidone. Calcium hydroxide was added to the resulting polymer solution in an amount sufficient to contain 95% of that present in the solution Neutralize hydrochloric acid. The solution then became Stored at 120 ° C. for 2 hours, the desired polymer being obtained. -

(XI) The desired polymer was prepared by adding ^{1,3-phenylene-2,2 f} -bis- [5-carboxy ~ (N-phenyl) -benzimidazoles of the following formula,

HOOC -

Γ COOH

with ^, V-diphenylmethane diisocyanate at 160-180 ° C in N-methylpyrrolidone polymerized.

Table 7 Structural units and inherent viscosity of the polymers

Structural unit

inn

OCHN -ι

0.95

309813/1082

(II) - + / oCHN

1.13

OQS «)

(III) 1 / oCHN -

1.53

(25J «)

(IV) -44 OCHN-

(20SS)

C0 (7Ca |

309813/1062

(VII)

(VIII)

(IX)

θθ

(70 «)

HHCO - // \\ tt- 0.63

CONHNHCO-

NHCO

(TOjQ 0.71

0.53

309813/1062

(X) - + OCNHNHOC ■

tX > Q

1.38

N - ^ ^ \ ^ CONH

) .58

309813/1062

Tabel

25th
26th
27
28
29
30th
31
32
.33
34
35

Conditions in the manufacture of the membrane polymer solvent additive

Example no. Art

Ht

Quantity art

(I)

0.65 10

(II) 0.66 10

(III) 0.66 10

(IV)

(V)

(VI)

0.69 15

0.65 10

0.55 IO

(VII) 0.59 .18

(VIII) 0.64 15

(IX) 0.62

(X)

(XI)

0.64 10

0.55 21

NMP NM? NMP

NMP NMP NMP NMP NIiP NMP NMP

Amount type amount

87 87 87 79 87 87

75

-80 90 86 73

LiCl • LiCl

LiCl

CaCl.

LiCl. UCl

LiCl

CaCl.

LiCl. CaCl.

LiCl

dry

Pouring _o v -

thickness (n) ^d) ° C / min.

320
320
350
220
320
32Ö
250
300
400
320
250

130 "IF

130

- "IF

125

17th

128 IS

130 15

13?

125

130

"IF

130

130

IF

130

IF

CJN ul

CD CD OQ

- 66 - Remarks;

1) parts by weight.

2) Casting was carried out at room temperature on a glass plate using a doctor blade.

3) NMR = N-methyl pyrrolidone.

3098 13/1062

Table 8

O ÖD KJ

Example no. (%) (l 25th '69 .6 \ f
73 26th 55.7 64 27 62.3 66 28 57.4, 53 29 58.0 62 30 · 6Ο.3 S5 31 65-9 74 ■ 52 71.0 85 33 51.0 48 34 61.5 62 35 50.3 71

Properties of the membranes

Water membrane concentration pressure. Water- water per- salt retention * thickness of the initial (kg / cm ² inflow meability holding capacity

solution *#
___ (%) '(kg / cm ² ) (l / m ² / h Wp (%)

Remarks *.

1.0 1.0 1.0 1.0 1.0 .1.0 3.5

Water content

95.7 89.6 93 * 8 71.4 97.9 99.1 98.8

94.5 98.6 92.4 99.5

Weight of the water contained in the membrane '

80 38.2 • 530 80 25.2 350 8o 42.5 590 80 28.8 4oo 80 20.3 282 80 13 * 5 187 I DO 24.3 325 8o 41.2 570 80 17.8 235 80 21.3 296 80 13.2 . 183

χ

Weight of the wet membrane
An aqueous NaCl solution was used as the starting solution.

Claims (9)

Claims denotes in which m and (n) represent 0 or 1, the two nitrogen atoms are bonded _{to two adjacent core carbon atoms of the group Ar 1 and Ar 2} denotes a monovalent aromatic group having up to 15 carbon atoms and in which (i) if (n) denotes 0, Ar ₁ denotes a trivalent aromatic group with up to 15 carbon atoms, Y - CONH-, -CONHNHCO-, -NHCONH- and / or -NHCNHNHC- it η 0 0 means, and when Y means -CONH- or -NHCNHNHCt, Il It 0 0 can Ar. either nitrogen or carbon atoms be bound by Y, (ii) if (n) means 1, is a single bond and Ar ^ is a tetravalent aromatic radical having up to 15 carbon atoms and Y is a group of the following 309813/1062 formula -C wherein, the two nitrogen atoms are bonded to adjacent core carbon atoms of the aromatic group Ar * and where Ar ·, a monovalent aromatic group with up to 15 carbon atoms means, and (iii) the divalent group represented by the above formula II is shown, bound in the polymer to the left or to the right, i.e. both in the left and in the right direction can be; (b) B is a single bond or a divalent organic bond Group means in which the average number of atoms excluding hydrogen atoms is not greater than 80 and where carbon atoms at the terminal ends stand, and wenh B means a single bond that is repeating units A represent groups expressed by the above formula II j (2) the parameter (Hp) of the hydrophilic property, expressed by the following formula of the linear polymer is at least 0.4 ^N H ^{+ 10N} I ^p ~ total number of atoms exclusively \ J) of the hydrogen atoms in the polymer where N _{H is} the number of hydrogen bonding units provided by the polar groups in the entire polymer and is expressed by the product of the number (N _A ) of hydrogen bonding groups in the entire polymer and their hydrogen bond strength (Gy), and N , means the number of ionic groups in the entire polymer, with the proviso that the 309813/1082 the number of ionic groups does not exceed 1 per 500 molecular weight of the polymer; (3) the solubility at 25 ° C of the linear polymer in a solvent such as Ν, Ν-dimethylacetamide, N-Methylpyrroll ~ don, dimethylsulphoxide and / or hexamethyl phosphoramide at least 7 wt -.%, Wherein the solvent or the solvent to may contain up to 5 wt .- # lithium chloride; and the linear polymer has a molecular weight sufficient to form a film. 2.) Permselective polymeric membrane according to claim 1, characterized in that that the substrate polymer as unit A has at least one kind of groups of the following formulas -Ar '^ Ar ₂ -COHN-Ar ", C- jj, -NHOC-Ar "-. contains, wherein Ar ^ and Ar "are a group of the following formula 309813/1062 Va or* , Vo means where R ^ is a hydrogen or halogenate on or a lower alkyl or lower "alkoxy group with 1 to. 3 carbon atoms, / 1 or 2 and Z is a single bond or an alkylene group with up to 4 carbon atoms, -0-, -S-, -SOg- or -CO- signifies, and if Z signifies a single bond, the formula (Vc) signifies a trivalent or tetravalent biphenyl group, and "..." in the aromatic group means a single bond in the case of Ar ¹ ^ and a hydrogen atom or a substituent R ^ in the case of Ar ".. ' J5.) Permselective polymeric membrane according to claim 1 or 2, characterized in that the linear substrate polymer as units B (1) Contains at least one kind of divalent organic groups selected from (i) aromatic hydrocarbon radicals ,, the benzene or Contain naphthalene nuclei, (ii) aliphatic hydrocarbon radicals, which are a cyclohexane, Contain cyclopentane or cyclobutane core, (iii) straight-chain or branched, saturated or unsaturated hydrocarbon radicals having 1 to 6 carbon atoms and (iv) 5- or 6-membered heterocyclic radicals containing oxygen, Contain nitrogen or sulfur and which can be condensed on a benzene nucleus, with carbon atoms 309813/1062 - T2 - are contained at both terminal ends in the divalent organic groups "or ^:; ; (2) (a) at least one di-, tri- or tetravalent organic Group in which hydrocarbon atoms are present at both terminal ends and those selected from (i) to (iv) above become and with (b) the organic groups on at least one of the following ■: ■■ "■ R. ■"; the groups -0-, -S-, -SO ₂ -, -CO-, -N- (where R is a hydrogen atom or an alkyl group with 1 to J carbon atoms or a phenyl group), -COHN- -CONHNHOC-, -NHCHN-, -CONHNHCOHN- and ^ N are bound, wherein the groups (1) and (2) can be substituted with a lower alkyl group of 1 to 4 carbon atoms ,, a lower alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a sulfonic acid . or carboxylic acid group, a salt of such an acid residue, a lower alkoxycarbpnyl group, a primary, secondary or tertiary amino group, an ammonium salt thereof or a quaternary ammonium base, and wherein in the units B, which are present in the entire polymer, the average number of atoms excluding the hydrogen atoms is no larger than 80. 4.) Permselective polymeric membrane according to one of claims to 2 # wherein the units A are a divalent group of the following Formula VI (VI) mean, wherein Ar ' ₂ and Ar ¹ ^, which are the same or different 309813/1042 can, a monovalent aromatic group of up to 15 carbon atoms the following formula VIrI or VI-2 mean, where Rg and R *, which can be the same or different, a hydrogen atom, an alkyl group with 1 to 1 carbon atoms, a halogen atom, a nitro group, a sulfonic acid or carboxylic acid group or a salt thereof, ρ is 1 or 2 and Z has the definitions given in the above formula Vc, and the units B are a divalent organic group of the following formula (VII) mean, where q ^ is an average content of the units (IUp
-W -) - fl- '* ^which are contained in ^{the polymer means} «S. and has a value of 0.2 to j5 moles per mole of the repeating units A, R ₂ and ρ has the definitions given above for formula VI-I and W -CONH- (which is also used in the 309813/1062 -COv can be arranged in the opposite direction), -0-, -SO-, N- (in which case the ot or ß ring is trivalent) ,. -CONHNHOC-, an alkylene group of 1 to 4 carbon atoms or N ——N denotes, in which X -0-, -S-, -NH-, or -C C -R- ν means. 5.) Permselective polymeric membrane according to one of claims 1 to 3, characterized in that the units A have at least one type of divalent O groups of the following formula -COHM -ι ^ Υ \ - (VIII-I) or - «HOC mean, in which Ar'g is given in the above formula VI Definition and the units B has at least one kind of atomic groups of the following formula IX \ (IX) 309813/1062 .. ■, ■ -75 - 22U908 mean, where q _{2 is} the average content _{: of} the units P means and a "value of 0 to 3 moles per mole of repeating units A and where Rp, ρ and W have the definitions given above for both formulas VI and VII. 6.) Permselective polymeric membrane according to one of claims 1 to 5 ι characterized in that the units A groups of the following formula X. (X) contain, in which Ar ' _{2 has} the definitions given above for' formula VI and the units B contain groups of the following formula, (XI) contain, wherein q ₂ , R ₂ , ρ and W have the definitions given above for formula IX. 7.) Process for the production of a permselective polymeric membrane, characterized in that a solution is partially solidified that contains (a) a linear polymer with an N-aryl-substituted benzimidazole structure, which contains the units A and B specified in claims 1 to 6 and 309813/1082 (b) an aprotic polar solvent that has the ability possesses to dissolve the linear polymers therein, preferably together with (c) a low molecular weight compound, the molecular weight of which does not exceed 500, and is soluble in the organic solvent (b) and the non-solvent (d) described below, the partial solidification being carried out to such an extent that the resulting partial Solidified membrane is self-sustaining or has self-sustaining properties, the partially solidified membrane is immersed in a non-solvent (d) for the linear polymer (a), the solvent being compatible with the organic solvent, (b) and at least are extracted $> of the organic solvent (b) or the organic solvent (b) and the compound with low molecular weight (c) that are left in the partially solidified membrane - 75 wt.. 8.) The method according to claim 7, characterized in that the solution containing the three components (a), (b) and (c) contains the compound (c) with low molecular weight in an amount which is less than 50 contains% of linear polymers (a) and the solution 50 to 93 wt - - wt .- ^, based on the linear polymer (a), the solution from 7 to 50 wt..% of organic solvent (b). 9.) The method according to claim 7, characterized in that the partially solidified membrane with self-supporting property, which was prepared from the solution containing the components (a) and (b), preferably with the compound (c) having a low molecular weight , is immersed in the non-solvent (d) at a temperature in the range from -2O ° C to 50 ⁰ C, wherein at least 80 wt .- * 5 of the organic solvent (a) or at least 8O gr-w.-jS of Each of the organic solvent (I)) and the low molecular weight compound (c) e: xlral; j pH become. 3U9813 / 106?